Electron Transfer Reactions Research Articles

Unlocking hierarchical hollow nanoblocks of NiMo sulfide with extended interlayer spacing of Mo-S units for high-performance supercapacitor

Molybdenum sulfide (MoS2) has been investigated as electrode of supercapacitor due to its unique structure. However, the restricted availability of active sites and sluggish behavior at the basal surface impede its improvement. Here we propose an unlocking hierarchical hollow strategy to synthesis the bimetallic sulfide heterostructures loaded on the ultrathin carbon (NiS/MoS2@UC). The unlocking hierarchical hollow structure and extended S-Mo layer provide interconnected channels for rapid electrolyte ion transport, while the heterojunction interface promotes the electron transfer and redox reaction. As a result, NiS/MoS2@UC − 2 exhibits a high specific capacitance of 616.7F g−1 at the current density of 1 A/g, which is approximately 10 times higher than that of MoS2@UC and 6 times higher than that of NiS@UC. Moreover, NiS/MoS2@UC − 2 demonstrates a high energy density of 7.7 Wh kg−1 at the power density of 300 W kg−1 with excellent cycling durability.

Evaluation of the Solid-Electrolyte Interphase Formation in a Bis(fluorosulfonyl)amide Based Ionic Liquid in the Presence Lithium Ion Using Different Redox Probes

The SEI formation in 0.5 M LiFSA/BMPFSA was investigated using different redox probes. The redox reaction of a metallocene and organic compound on a Pt electrode were investigated by cyclic voltammetry in BMPFSA and 0.5 M LiFSA/BMPFSA. Cyclic voltammograms were taken after holding the electrode at different potentials for 1 h. The cyclic voltammograms were unchanged in BMPFSA, indicating that BMPFSA was stable in the measured potential range and that the redox reaction was not affected by a change in the electric double layer structure. On the other hand, peak shifts were observed in the presence of Li+ at potentials more negative than –1.1 V vs. Ag|Ag(I), attributed to a decrease in the electron transfer rates and indicating that the SEI formation promoted by the interaction between Li+ and FSA– affects the redox reactions not only of metallocene but also of organic compounds that undergo outer sphere electron transfer reactions.

Solvent Effects on Spin-Orbit Charge-Transfer Intersystem Crossing in Aryl-Substituted Boron-dipyrromethene Donor-Acceptor Dyads.

In heavy-atom-free organic molecules, the rate of triplet generation through charge recombination, as dictated by the El-Sayed rule, can be enhanced by 101-102 times compared with the rate of spontaneous spin flipping between π-π* orbitals. This mechanism is known as the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). Within the framework of the SOCT-ISC mechanism, facilitating the generation of charge-separated (CS) states and suppressing the spin-allowed direct charge recombination to the ground state are pivotal for maximizing the efficiency of generating localized triplet states. Herein, a series of orthogonal aryl-substituted boron-dipyrromethene dyads were studied by time-resolved spectroscopy to unravel the multichannel competitive relationships in the SOCT-ISC mechanism. The energy level of the electron donor and the stabilization of the solvent effect to the charge-transfer state are reflected in the Gibbs free energy changes of the electron transfer and recombination reactions, leading to significantly different triplet quantum yields. Additionally, solvation-induced electronic coupling changes in excited states lead to the fact that the spin-allowed charge recombination rate cannot be well simply predicted by the Marcus inverted region but has to consider the specific excited-state dynamics in optimizing the proportion of triplet generation channels based on charge recombination.

Metal Organic Frameworks‐Derived NiO/NiCo2O4 Heterostructures for Effective Methanol Oxidation Reaction

AbstractThe electrochemical process of methanol oxidation reaction (MOR), which is closely associated with electrochemical production of formate and hydrogen, is considered a highly viable avenue for advancing renewable energy technologies. Nevertheless, the development and creation of affordable, effective, and durable electrocatalysts for MOR continue to present significant obstacles. In this study, a hierarchical porous NiO/NiCo2O4/NF electrode is fabricated through the integration of solvothermal and thermal oxidation treatments of Ni‐MOF‐74 and NiCo‐Asp. After thoroughly assessing the electrochemical performance for MOR, NiO/NiCo2O4/NF demonstrates a significant current density of 140 mA cm−2 at 1.6 V (vs. RHE) and a tafel slop of 45.0 mV·dec−1 in 1 M KOH and 0.5 M methanol. The excellent performance of MOR can be ascribed to the hierarchical porous nature that enhances mass and electron transport while offering numerous active sites for electrocatalytic reactions. Additionally, the hetero interface between NiO and NiCo2O4 could further enhance electron transfer rate and reaction kinetics for the MOR. The developed NiO/NiCo2O4/NF electrode shows potential as a viable and economical alternative to Pt‐based electrocatalysts for MOR‐based applications.

Redox kinetics of multi-electron transfer reactions of polyoxometalates (POMs) relevant to electrochemical devices

The formal equilibrium potential (E0′) and heterogeneous rate constant (k0) are characteristics of any electron-transfer reaction. The estimation of these characteristics for very fast multiple electron-transfer reactions of polyoxometalates (POMs) relevant to various applications including redox flow batteries, hydrogen storage materials, and electrocatalysis is highly challenging by the conventional electrochemical methods. Therefore, E0′and k0 (k0∼10–2 cm sec‑1) of such reactions (for e.g., that of tungstosilicic acid (SiW12) and phosphotungstic acid (PW12)) separated by small potential windows are estimated from the background current free higher harmonic response of large-amplitude AC voltammetry. For SiW12/PW12 redox species, the E0′ values of processes 1, 2, and 3 estimated from the minima of second harmonic response are -0.326/-0.127, -0.530/-0.380 and -0.691/-0.701 (V vs. Ag/AgCl), respectively. The k0 values of the first redox process (P1) of SiW12 (SiW12/ SiW12-,4.8 × 10–2 cm sec‑1) and PW12 (PW12/PW12-,5.2 × 10–2 cm sec‑1) estimated from the large-amplitude AC voltammetry are further validated through the impedance measurement (2.1 × 10–2 and 2.4 × 10–2 cm sec‑1). The uniqueness of large-amplitude AC voltammetry over conventional DC techniques and impedance spectroscopy is illustrated. The relevance of k0 values in the context of electrocatalytic processes and RFBs system is also presented.

A study of electrochemiluminescence mechanism of Rubrene/TPrA system in an aqueous solution via stochastic collision electrochemistry in an emulsion reactor

BackgroundElectrochemiluminescence (ECL) is an electrochemically induced process in which radicals generated at the electrode surface undergo exergonic electron transfer reaction to form excited states and luminesce. ECL, with high sensitivity and superior spatiotemporal control, has been widely applied in bioanalysis and light-emitting devices. The ECL signal of rubrene (Rub) was observed in Rub/TPrA oil-in-water (o/w) emulsions, which was inconsistent with the theory of ion-transfer coupled electron-transfer in Rub emulsion droplets, and the conventional ECL mechanism in Rub/TPrA system couldn't explain this phenomenon. ResultsChoosing the toluene oil-in-water emulsion droplets as reactors, we put forward and verified a new ECL mechanism of Rub in aqueous solution on the basis of cyclic voltammograms, single-entity electrochemistry, ECL detection techniques and COMSOL finite element simulation. The new mechanism involved that Rub was reduced to Rub•- by the highly reducing species TPrA•, Rub•- was then oxidized to the excited state Rub∗ by the stable intermediate TPrA•+, and finally Rub∗ was inactivated by emitting photons. In simulation, the standard oxidation rate constant of TPrA in the emulsion droplets was deduced as 1.5 × 10−4 cm/s, and the deprotonation rate of TPrA•+ was about 200 s−1. Besides, emulsion droplets colliding on Au ultramicroelectrode (UME) were found to be able to amplify ECL signals. SignificanceThe newly proposed ECL mechanism of Rub/TPrA emulsion reactors broke the solubility problem of Rub in an aqueous, promoting the research and application of the organic luminophore Rub in bioanalysis. With the ECL signals amplification capability, the o/w emulsion reactors are promising to future design of ECL biosensors with higher sensitivity.

Direct Observation of the Reactivity of Electrons toward Gold Nanoparticles in Aqueous Solution.

The catalytic activity of gold nanoparticles (AuNPs) has been widely acknowledged; however, Au NPs are considered to be highly inert as radiosensitizers in biological systems. This apparent discrepancy across different fields complicates the understanding of their interfacial reactivity, particularly in terms of electron transfer reactions. Here, we employ pulse radiolysis to determine the rate constants for the reactions of electrons with AuNPs in aqueous solution. Our investigation of AuNPs with different sizes and surface modifications demonstrates the potential influence of the AuNPs design on electron transfer reactions. These findings address long-standing mechanistic contradictions and underscore the significance of interfacial electron dynamics on AuNPs in both catalytic and biological processes.

Synergistic photoelectrochemical detection of Cd2+ with carbon-bismuth oxybromide composites: Mechanistic insights from DFT calculations

The existences of hazardous heavy metals like cadmium (Cd) in water bodies necessitates rapid, accurate on-site detection strategies. Herein, a novel photoelectrochemical scheme for sensitive detection of Cd2+ was proposed based on the hybrid carbon-bismuth oxybromide materials (C/Bi4O5Br2 and CNTs/BiOBr). The effects of ultraviolet light (UV-light) illumination during the Cd2+ deposition and desorption stages were analyzed, revealing enhanced photocurrent responses and detection sensitivity compared with those non-illumiantion. The optimal sensitivity of 0.42079 μA/ppb (C/Bi4O5Br2 under both deposition and desorption stages) and 0.15634 μA/ppb (CNTs/BiOBr under desorption stage only) were observed with UV illumination within a Cd2+ range of 10–100 ppb. Density functional theory calculation elucidated that Cd2+ adsorption on the semiconductor surface reduced the badgaps of Bi4O5Br2 and BiOBr, which would benefit electron transfer and redox reactions. Additionally, the interaction between Cd and the semiconductor produced a Schottky barrier, which prolonged the lifetime of the photo-generated electron-hole pairs, where the electrons migrated on the semiconductor surface formed electron capture traps and induced band bending, therefore facilitated the electrons in the conduction band to react with Cd2+ deposited on the electrode surface. The study provides mechanistic insights into the photoelectrochemical processes in enhancng precise and sensitive on-site heavy metal ions detection.

Integrated electrochemical and chemical system for ampere-level production of terephthalic acid alternatives and hydrogen

2,5-Furandicarboxylic acid (FDCA), a critical polymer platform molecule that can potentially replace terephthalic acid, coupled hydrogen coproduction holds great prospects via electrolysis. However, the electrosynthesis of FDCA faces challenges in product separation from complex electrolytes and unclear electrochemical and nonelectrochemical reactions during the 5-hydroxymethylfurfural (HMF) oxidation. Herein, an electrochemical/chemical integrated system of alkaline HMF-H2O co-electrolysis is proposed, achieving distillation-free synthesis of high-purity FDCA by acidic separation/purification and hydrogen coproduction. This system achieves ampere-level current densities of 812 and 1290 mA cm−2 at potentials of 1.50 and 1.60 V, with nearly 100% FDCA yield and HMF conversion in only 6 min at 1.50 V. The electrooxidation of HMF involves a coupling of electrochemical and nonelectrochemical reactions, wherein the aldehyde group is dehydrogenated and oxidized, followed by dehydrated and oxidized of the hydroxyl group, ultimately forming FDCA. Concurrently, nonelectrochemical reactions of intermolecular electron transfer occur in HMF and aldehyde group-containing intermediates.

Schiff base substituted non-peripheral symmetrical cupper, cobalt, and manganese phthalocyanines: Synthesis, design, electrochemistry, and spectroelectrochemistry

Novel CoII (nANTHCoPc), CuII (nANTHCuPc), and MnIIICl (nANTH-MnClPc) phthalocyanines were obtained by substituting the 3-(4-((1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylimino)methyl)phenoxy) Schiff base compound (nANTHOH) obtained by the acid-catalyzed condensation reaction of 4-aminoantipyrine and 4-hydroxybenzaldehyde at non-peripheral positions. By using various spectroscopic techniques, (NMR, MALDI-TOF, FT-IR, and UV–Vis), the structures of green-colored phthalocyanine compounds and precursor phthalonitrile compounds were identified. The electrochemical responses of cobalt (II) (nANTHCoPc), cupper (II) (nANTHCuPc), and manganese (III) (nANTH-MnClPc) phthalocyanines were determined, and their redox responses were analyzed based on the different metal centers. The results indicated that using redox-active Co2+ and Mn3+ cations instead of Cu2+enhanced the redox richness of the complexes due to the observation of extra metal-based electron transfer reactions in addition to the Pc-based ones. In-situ spectroelectrochemical analyses of the complexes were used to support the peak assignments of the redox processes and the spectrum and color of the electrogenerated species during the redox reactions. Supported these redox mechanisms. Multi-electron transfer processes and distinct color changes during these processes indicate the possible usage of these complexes in various electrochemical and opto-electrochemical processes. Metal-based electron transfer reactions illustrated different spectral changes than those of the Pc-based ones, and these spectral changes significantly differed the color of the anionic and cationic species.

Simulating Cavity-Modified Electron Transfer Dynamics on NISQ Computers.

We present an algorithm based on the quantum-mechanically exact tensor-train thermo-field dynamics (TT-TFD) method for simulating cavity-modified electron transfer dynamics on noisy intermediate-scale quantum (NISQ) computers. The utility and accuracy of the proposed methodology is demonstrated on a model for the photoinduced intramolecular electron transfer reaction within the carotenoid-porphyrin-C60 molecular triad in tetrahydrofuran (THF) solution. The electron transfer rate is found to increase significantly with increasing coupling strength between the molecular system and the cavity. The rate process is also seen to shift from overdamped monotonic decay to under-damped oscillatory dynamics. The electron transfer rate is seen to be highly sensitive to the cavity frequency, with the emergence of a resonance cavity frequency for which the effect of coupling to the cavity is maximal. Finally, an implementation of the algorithm on the IBM Osaka quantum computer is used to demonstrate how TT-TFD-based electron transfer dynamics can be simulated accurately on NISQ computers.

Graphene with suitable-size nitrogen-doped cavity being an excellent photocatalyst for proton-coupled electron transfer in water splitting

Aiming to attain porous carbon nitride photocatalysts with high specific surface area, abundant active sites, broad absorption range and effective electron-hole separation, we remove carbon rings from graphene and replace all the edge carbon atoms of the cavity with nitrogen atoms. The accurate electronic structures and exciton properties of the proposed materials are revealed by the ab initio many-body Green's function theory. Computational results show that the absorption of the designed materials can cover both the visible and the near-infrared light region. The exciton binding energies of the materials are one order of magnitude lower than those of the typical two-dimensional photocatalyst graphitic carbon nitride. Due to the formation of hydrogen bonds between pyridinic nitrogen atoms and water molecules during water splitting, the key excited-state proton-coupled electron transfer reactions are barrierless. These findings could serve as guidelines for the realization of high-performance metal-free two-dimensional photocatalysts.

Thermodynamic Factors Controlling Electron Transfer among the Terminal Electron Acceptors of Photosystem I: Insights from Kinetic Modelling.

Photosystem I is a key component of primary energy conversion in oxygenic photosynthesis. Electron transfer reactions in Photosystem I take place across two parallel electron transfer chains that converge after a few electron transfer steps, sharing both the terminal electron acceptors, which are a series of three iron-sulphur (Fe-S) clusters known as FX, FA, and FB, and the terminal donor, P700. The two electron transfer chains show kinetic differences which are, due to their close geometrical symmetry, mainly attributable to the tuning of the physicochemical reactivity of the bound cofactors, exerted by the protein surroundings. The factors controlling the rate of electron transfer between the terminal Fe-S clusters are still not fully understood due to the difficulties of monitoring these events directly. Here we present a discussion concerning the driving forces associated with electron transfer between FX and FA as well as between FA and FB, employing a tunnelling-based description of the reaction rates coupled with the kinetic modelling of forward and recombination reactions. It is concluded that the reorganisation energy for FX- oxidation shall be lower than 1 eV. Moreover, it is suggested that the analysis of mutants with altered FA redox properties can also provide useful information concerning the upstream phylloquinone cofactor energetics.

Quantitative and mechanistic elucidation of the reactive oxygen species for effective sulfamethoxazole removal in heterogeneous peroxymonosulfate activated by MOFs-derived cladding structure CoZn/NC@UiO

In cobalt-based catalyst/peroxymonosulfate (PMS) systems, the key issues are the leaching of metals and the stability of catalysts. In this study, a NH2-UiO-66 cladded CoZn/NC catalyst was synthesized for efficient degradation of sulfamethoxazole (SMX) using activated PMS. The removal efficiency of SMX could achieve 100% within 30 min. The leaching of Co2+ was inhibited to 0.05 ppm and the anti-interference and cyclic stability of the catalyst were enhanced by the NH2-UiO-66 shell. In addition, the quenching experiment, electron paramagnetic resonance (EPR) technique and probe experiment were used to analyze the reactive oxygen species (ROSs) qualitatively and quantitatively. The findings demonstrated that singlet oxygen (1O2) had the highest steady-state and cumulative concentration. However, 1O2 could only participate in the degradation of SMX through single electron transfer or addition reaction, resulting in a lower second-order rate constant of the SMX reaction with 1O2. Sulfate radical (SO4·-) contributed the most to the degradation of SMX due to the high reactivity of the sulfonamide structure in SMX to SO4·-. Finally, possible pathways for SMX degradation were proposed. The two primary mechanisms of SMX degradation were S-N cleavage and amino hydroxylation/oxidation. The toxicity of most of the intermediates was less than that of SMX through ecological structure–activity relationship analysis. Overall, a novel approach to synthesize low leaching and efficient cobalt based catalyst was put forward, and the activation mechanism of PMS was also revealed.

Tailoring a novel all-in-one host-guest solid-state electrochemiluminescence platform for selective detection of spermine using cucurbit-[6]-uril modified [Ru(bpy)3]2+ electrode

Herein, a novel solid-state electrochemiluminescence (ECL) based on electrochemically incorporated [Ru(bpy)3]2+ on nafion modified glassy carbon electrode ([Ru(bpy)3]2+-Nafion/GCE) followed by chemisorption of cucurbit-[6]-uril (CB-[6]) on Ru(bpy)3]2+-Nafion/GCE (as CB-[6]-[Ru(bpy)3]2+-Nafion/GCE) has been developed for selective sensing of spermine (SPM) which belongs to the class of aliphatic biogenic amines and overexpression of SPM is associated with several cancers, particularly “Prostate Cancer” (PCa). Interestingly, the ECL emission of [Ru(bpy)3]2+ be enhanced significantly in the presence of CB-[6] modified [Ru(bpy)3]2+-Nafion/GCE. This is due to inherent ability of CB- [6] act as a co-reactant accelerator. Upon the addition of SPM, the ECL emission was further enhanced due to electron transfer reaction between SPM and [Ru(bpy)3]3+. Selectivity of the proposed ECL sensor towards SPM arises from the host-guest interaction between the CB-[6] and SPM, follows the anodic co-reactant ECL reaction (oxidative reduction mechanism) by confirmation of electrochemical and spectroscopic results like electron spin resonance (EPR) and ECL spectra. The proposed solid-state ECL sensor platform is selectively detect to SPM for a linear range of 10 nM - 5 mM with detection limit (LoD) of 1.4 nM at physiological pH conditions. In addition, the developed ECL platform of CB-[6]-[Ru(bpy)3]2+-Nafion/GCE has been successfully verified to the sensing of SPM in the urine sample, proving the practicability of the proposed sensor is suitable for clinical analysis.

Towards electrochemical regeneration of redox photocatalysts? The example of the tris(2,2′-bipyridine)ruthenium(II)/methylviologen system

The regeneration of redox photocatalysts usually requires the use of sacrificial reagents that are added to the medium in stoichiometric amounts, either as an electron donor or as an electron acceptor, to act as an electron relay to the photocatalyst to ensure its effective regeneration. In the present work, we consider the possibility of direct electrochemical regeneration of the catalyst using a model system made of tris(2,2′-bipyridine)ruthenium(II) ([Ru(bpy)3]2+) as photosensitizer and methylviologen (MV2+) as quenching substrate. Based on hydrodynamic amperometry experiments, we demonstrate that this can indeed be possible provided that appropriate potential values are applied to ensure the electrochemical reduction of [Ru(bpy)3]3+ back to [Ru(bpy)3]2+ while avoiding interfering processes arising from electron transfer reactions involving the quencher and/or the products/intermediates generated in the course of the photocatalytic event. Furthermore, using EDTA as a sacrificial electron donor, we show that photocurrents can also be exploited for regenerating the quenching substrate by reduction of the reaction product MV+ (back into MV2+).

Novel Etch-Resistant Molecular Glass Photoresist Based on Pyrene Derivatives for Electron Beam Lithography.

Novel t-butyloxycarbonyl-protected molecular glass photoresists with pyrene as the core (Pyr-8Boc and Pyr-4Boc) were designed and synthesized. The thermal stability and film-forming ability were measured to assess their applicability for lithography. Pyr-Boc (Pyr-8Boc and Pyr-4Boc) photoresists were evaluated by high-resolution electron beam lithography (EBL), acting as chemically amplified resists. Pyr-4Boc showed a better lithography performance, achieving 25 nm line/space patterns at the dose of 50 μC/cm2. Under SF6/O2 plasma, the etch selectivity of the Pyr-4Boc photoresist to silicon was 12.3, which is twice that of the commercially available poly(methyl methacrylate) photoresist (950 k). The lithography mechanism of EBL was further investigated. Theoretical calculations of HOMO/LUMO orbital energies, cyclic voltammetry, and fluorescence quenching experiments were conducted to confirm the electron-transfer reactions between the Pyr-Boc and photoacid generator. The study provides an option of high sensitivity and etch-resistant photoresist for EBL.

Photophysics and Excited State Reactions of [Ru(bpy)2dppn]2+: A Computational Study.

In this work, we used DFT and TD-DFT in the investigation of the structural parameters and photophysics of the complex [Ru(bpy)2dppn]2+ (dppn = benzo[i]-dipyrido[3,2- a:2',3'-c]phenazine) in water, and its suitability as a photosensitizer (PS) in photodynamic therapy (PDT). For that, the thermodynamics of electron transfer (ET) and energy transfer (ENT) reactions in the excited state with molecular oxygen and guanosine-5'-monophosphate (GMP) were investigated. The overall intersystem crossing (ISC) rate constant was approximately 1012 s-1, indicating that this process is highly favorable, and the triplet excited states are populated. The triplet excited states are known to lead to photoreactions between the PS and species of the medium or directly with nucleobases. Here, we show that the Rudppn complex can react favorably to oxidize the GMP and generate singlet oxygen. Furthermore, this complex can also act as an intercalator between DNA base pairs and undergo dual-channel reactions. It has been proposed that the T2 excited state is responsible for oxidizing the GMP, but we show that T1 is thermodynamically capable of undergoing the same reaction. In this sense, docking simulations were carried out to investigate further the interactions of the Rudppn complex with a DNA fragment.

Improving the electrocatalytic activity of the copper (II) metal-organic framework by functionalized imidazolate linker and functionalized carbon nanoparticles for detection of acyclovir

With the aim of expansion of nanocomposite materials in electrochemical sensors, the use of nanostructures as the electrode modifier has been shown to improves the kinetics of the electron transfer reactions and consequently increases the sensitivity of the sensors. So, in this study, a new electrochemical sensor was fabricated by using the nanocomposite of copper (II) metal–organic framework with functionalized imidazolate linker [Cu3(BTC)2-2-MIM] and cationic functionalized carbon nanoparticles (CFCNPs) at the glassy carbon electrode (GCE); Cu3(BTC)2-2-MIM/CFCNPs/GCE. The as prepared nanocomposite; Cu3(BTC)2-2-MIM/CFCNPs was characterized using various instrumental techniques. To identify the capabilities and electrocatalytic activity of the synthesized nanocomposite in analytical chemistry, it was used as an electrochemical modifier along with suitable electrochemical techniques. In this regard, the prepared modified electrode; Cu3(BTC)2-2-MIM/CFCNPs/GCE was utilized to the electrooxidation and determination of the acyclovir (ACR) in NaOH solution. Under optimal experimental conditions, the Cu3(BTC)2-2-MIM/CFCNPs/GCE showed low detection limit (0.24 µM) over the concentration ranges of 2.49–84.28 μM of ACR. On the other hand, the present sensor has robust stability, good reproducibility, high selectivity and sensitivity (5.907 µAµM−1 cm−2) in electrodetermination of ACR. Also, the diffusion coefficient of ACR (DACR = 9.25 × 10−6 cm2 s−1), the transfer coefficient (α = 0.34) and catalytic rate constant (kcat = 10.1 × 105 cm3 mol−1 s−1) of ACR electrooxidation reaction were estimated at the surface of modified electrode in NaOH solution. Finally, the Cu3(BTC)2-2-MIM/CFCNPs/GCE was applied as a promising and low-cost sensor for determination of the ACR in actual pharmaceutical formulations and biological samples.

Highly sensitive electrochemiluminescence sensing platform based on copper nanoclusters synthesized via a DNA nanoribbon template for the detection of cancer cells

Herein, we presented a simple ultra-sensitive "on-off-on" electrochemiluminescence (ECL) biosensor that uses copper nanoclusters (CuNCs) synthesized via a DNA nanoribbon (DNR) template (DNR-CuNCs) as a sensing platform coupled with target-cycle amplification for the sensitive and rapid detection of cancer cells that overexpress proteins. DNR templated DNR-CuNCs, a well-ordered ECL emitter, was integrated into the nucleic acid framework structure to self-assembly, which enhanced the ECL intensity benefit from reduced band gap and accelerated electron transfer reaction of CuNCs. Additionally, an optimized exonuclease III (Exo III)-assisted cycle amplification method was introduced to efficiently convert trace target biomarkers into a substantial output of DNA, significantly improving target conversion efficiency and boosting the ECL signal. Consequently, MUC1 proteins were sensitively detected by the ECL biosensor throughout a broad concentration range, from 1 fg·mL−1 to 1 ng·mL−1, with a low limit of detection (LOD) of 0.061 fg·mL−1, and successfully detected MUC1-overexpressing cancer cells (using MCF-7 cancer cells as a model), accurately identifying MCF-7 cells in the concentration range of 10–100,000 cells·mL−1 with a LOD of 5 cells·mL−1. This research, for the first time, introduced a DNR-CuNCs ECL biosensor for the highly sensitive detection of living cells and their associated surface proteins. The detection of biomarker proteins and specific cells is greatly promising by applying this simple, sensitive, and specific strategy.